JP3162539B2 - Method of manufacturing ceramic wiring board having conductor formed by conductor paste - Google Patents
Method of manufacturing ceramic wiring board having conductor formed by conductor pasteInfo
- Publication number
- JP3162539B2 JP3162539B2 JP10510593A JP10510593A JP3162539B2 JP 3162539 B2 JP3162539 B2 JP 3162539B2 JP 10510593 A JP10510593 A JP 10510593A JP 10510593 A JP10510593 A JP 10510593A JP 3162539 B2 JP3162539 B2 JP 3162539B2
- Authority
- JP
- Japan
- Prior art keywords
- conductor
- paste
- mullite
- component
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004020 conductor Substances 0.000 title claims description 105
- 239000000919 ceramic Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 43
- 229910052863 mullite Inorganic materials 0.000 claims description 43
- 239000000843 powder Substances 0.000 claims description 28
- 238000005245 sintering Methods 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 239000010937 tungsten Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000004080 punching Methods 0.000 claims description 3
- 238000004017 vitrification Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000010304 firing Methods 0.000 description 10
- 239000012752 auxiliary agent Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008602 contraction Effects 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- -1 respectively Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Landscapes
- Conductive Materials (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Printing Elements For Providing Electric Connections Between Printed Circuits (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、導体ペーストによっ
て導体を形成したセラミック配線基板の製造方法に関す
る。 The present invention relates to a conductive paste.
Manufacturing method of ceramic wiring board with conductor formed
You.
【０００２】[0002]
【従来の技術】従来の多層配線基板は、アルミナ等を主
成分とするセラミックスからなり、板形状の複数枚の絶
縁層と、各絶縁層の主表面にタングステン、モリブデン
等の高融点金属にて形成された各種配線パターンとを備
えている。2. Description of the Related Art A conventional multilayer wiring board is made of ceramics containing alumina or the like as a main component, and has a plurality of plate-shaped insulating layers and a main surface of each insulating layer made of a high melting point metal such as tungsten or molybdenum. And various wiring patterns formed.
【０００３】このような多層配線基板は、次の手順で製
造される。まず、アルミナ等のセラミックス粉末を主成
分とするグリーンシートの表面に、タングステンＷ等の
導体ペーストを所定パターンにスクリーン印刷して、各
配線パターンを形成する。そして、打ち抜きによってグ
リーンシートに貫通孔を設け、その中に導体ペーストを
充填する。次にこれらグリーンシートを積層し、圧力下
で接着する。その後積層体が１５００℃前後の高温で焼
成され、その表面にＮｉ鍍金が施されてセラミックス多
層配線基板となる。かくして貫通孔に充填された導体ペ
ーストは、導体柱となって各層の配線を電気的に接続す
る。[0003] Such a multilayer wiring board is manufactured in the following procedure. First, a conductor paste such as tungsten W is screen-printed in a predetermined pattern on the surface of a green sheet mainly composed of a ceramic powder such as alumina to form each wiring pattern. Then, a through hole is formed in the green sheet by punching, and a conductive paste is filled therein. Next, these green sheets are laminated and adhered under pressure. Thereafter, the laminate is fired at a high temperature of about 1500 ° C., and its surface is plated with Ni to form a ceramic multilayer wiring board. The conductive paste filled in the through-holes thus serves as a conductive pillar to electrically connect the wiring of each layer.
【０００４】尚、Ｎｉ鍍金する前に又はＮｉ鍍金に代え
て、基板の表面にＴｉ、Ｃｒ等の活性金属をスパッタリ
ングして薄膜の高密度配線を形成することもある。とこ
ろで、近年、信号伝播速度を速くすることと、集積回路
ＩＣの接続不良及び剥離を未然に防止することのため
に、高密度ＩＣパッケージの多層基板中の絶縁層とし
て、アルミナ系セラミックスに代えてムライト系セラミ
ックスを用いようとする提案がなされている（特公昭５
７−２３６７２号公報，特開昭５５−１３９７０９号公
報）。[0004] Before or instead of Ni plating, an active metal such as Ti or Cr may be sputtered on the surface of the substrate to form a thin high-density wiring. By the way, in recent years, in order to increase the signal propagation speed and to prevent the connection failure and peeling of the integrated circuit IC, the alumina-based ceramic is used as an insulating layer in the multilayer substrate of the high-density IC package. A proposal to use mullite ceramics has been made (Japanese Patent Publication No. Sho 5)
7-23672, JP-A-55-139709).
【０００５】すなわち、電気信号の伝播遅延時間は、配
線導体をとりまく絶縁層の誘電率の平方根に比例するの
で、比誘電率の小さいムライトを絶縁層の主成分として
信号の高速化を達成しようとするのである。また、集積
回路ＩＣが半導体シリコンよりなるものの場合、シリコ
ンの熱膨張係数が３．５×１０-6／℃であるから、これ
と熱膨張差の小さいムライトをＩＣ搭載部の絶縁層の主
成分とすることにより、ＩＣ接続部分の熱応力を軽減し
ようとするのである。That is, since the propagation delay time of an electric signal is proportional to the square root of the dielectric constant of the insulating layer surrounding the wiring conductor, an attempt is made to achieve a high-speed signal by using mullite having a small relative dielectric constant as a main component of the insulating layer. You do it. Further, when the integrated circuit IC is made of semiconductor silicon, since the thermal expansion coefficient of silicon is 3.5 × 10 −6 / ° C., mullite having a small thermal expansion difference from this is used as the main component of the insulating layer of the IC mounting portion. By doing so, the thermal stress at the IC connection portion is reduced.
【０００６】このように絶縁層としてムライト系セラミ
ックスを用いるために、配線導体に用いられる金属ペー
ストについて、ムライト系セラミックスとの接着強度及
びムライト系セラミックスとの同時焼結の可能性が検討
されている。例えば、特開昭６２−１７２７８４号公報
には、高融点金属にシリカ−アルミナ−マグネシア系の
焼結助剤を添加してなる導体ペーストが開示されてい
る。また、特開平２−１３３３８３号公報には、作製過
程での還元温度の異なる２種類のタングステン粉末を配
合してなる導体ペーストが開示されている。In order to use the mullite ceramic as the insulating layer, the bonding strength of the metal paste used for the wiring conductor with the mullite ceramic and the possibility of simultaneous sintering with the mullite ceramic have been studied. . For example, Japanese Unexamined Patent Publication (Kokai) No. 62-172784 discloses a conductor paste obtained by adding a silica-alumina-magnesia sintering aid to a high melting point metal. Further, Japanese Patent Application Laid-Open No. 2-133383 discloses a conductor paste comprising two kinds of tungsten powders having different reduction temperatures in a production process.
【０００７】[0007]
【発明が解決しようとする課題】特開昭６２−１７２７
８４号公報に記載された技術は、導体金属表面の濡れ性
を良くすることによって、ムライト系セラミックスに用
いられている充分な量の焼結助剤を、導体ペーストに浸
透させ、ムライトセラミックスと導体金属との結合並び
に導体柱の緻密化を達成しようとするものである。Problems to be Solved by the Invention JP-A-62-1727
The technique described in Japanese Patent Publication No. 84 is to improve the wettability of the conductor metal surface so that a sufficient amount of the sintering aid used for the mullite ceramics is penetrated into the conductor paste, and the mullite ceramic and the conductor It is intended to achieve bonding with metal and densification of the conductor pillar.
【０００８】また、特開平２−１３３３８３号公報に記
載された技術は、還元温度によって焼成収縮率の異なる
点に着目し、タングステン粉末の配合割合を適切な範囲
に選定することによって、導体柱全体の収縮量をムライ
トセラミックスの収縮量に整合させようとするものであ
る。The technique described in Japanese Patent Application Laid-Open No. Hei 2-133383 focuses on the point that the firing shrinkage differs depending on the reduction temperature, and selects the compounding ratio of tungsten powder in an appropriate range, thereby reducing the entire conductor column. Is intended to match the shrinkage amount of the mullite ceramic.
【０００９】しかし、前者の導体ペーストをグリーンシ
ートの貫通孔に充填して形成した導体柱は、導体ペース
トの焼成収縮率とグリーンシートの焼成収縮率とが大き
く相違するために、ムライト絶縁層との間に大きな間隙
を生じることが判った。従って、その導体柱と内部配線
との間で断線や気密不良を生じる。また、表面に露出す
る導体柱の場合、スパッタリングで薄膜を形成すること
が困難となる。However, the former conductive paste formed by filling the through holes of the green sheet with the conductive paste has a large difference between the firing shrinkage of the green paste and the firing shrinkage of the green paste. It was found that there was a large gap between the two. Therefore, disconnection and poor airtightness occur between the conductor pillar and the internal wiring. Further, in the case of a conductor pillar exposed on the surface, it is difficult to form a thin film by sputtering.
【００１０】一方、後者の導体ペーストは、収縮率を微
調整することは可能であるが、タングステン粉末の種類
が限定されているために、直径の大きな貫通孔に充填さ
れて焼成された場合、充分に焼結しないことが判った。
すなわち、後者の導体ペーストから形成された導体柱
は、焼結不十分のために緻密な導体柱が得られず、また
あまり収縮しない。従って、平面方向の隣の導体柱と突
っ張り合い、その中間に存在するムライト絶縁層を変形
させる。また、導体柱のすぐ上に積層された絶縁層を突
き上げ、いわゆるデラミネーションすなわち層間亀裂を
生じる。それらの結果、表面配線の精度を劣化させた
り、気密不良を生じさせたりする。[0010] On the other hand, the latter conductor paste can finely adjust the shrinkage, but because the type of tungsten powder is limited, when it is filled in a through hole having a large diameter and fired, It was found that it did not sinter sufficiently.
In other words, the conductor pillars formed from the latter conductor paste do not provide a dense conductor pillar due to insufficient sintering and do not shrink much. Therefore, the mullite insulating layer located in the middle of the conductor pillar is in contact with the adjacent conductor pillar in the plane direction and is deformed. In addition, the insulating layer stacked right above the conductor pillar is pushed up, so-called delamination, that is, interlayer cracking occurs. As a result, the accuracy of the surface wiring is deteriorated, or poor airtightness is caused.
【００１１】本発明の目的は、上記の問題点を解決し、
ムライトの焼成収縮率と整合する収縮率を有し且つ低抵
抗の導体ペーストを提供し、そのような導体ペーストを
用いて導体を形成し、断線及び気密不良が生じにくく、
しかも高精度に表面配線を形成できるセラミック配線基
板を提供することである。An object of the present invention is to solve the above problems,
A conductor paste having a shrinkage rate matching the sintering shrinkage rate of mullite and having a low resistance is provided, and a conductor is formed using such a conductor paste , and disconnection and poor airtightness are less likely to occur,
Moreover, it is an object of the present invention to provide a ceramic wiring board on which surface wirings can be formed with high accuracy.
【００１２】[0012]
【課題を解決するための手段】その手段は、主成分とし
てのムライト粉末及びガラス化可能な焼結助剤を含有す
るグリーンシートを準備し、そのグリーンシートを打ち
抜いて貫通孔を設け、この貫通孔の中に、導体成分とム
ライト粉末とガラス化可能な助剤成分とを含み、ビヒク
ルによってペースト状に調製された導体ペーストを充填
した後、焼成することを特徴とするセラミック配線基板
の製造方法であって、ムライト粉末の含有量が、そのム
ライト粉末と導体成分との合計量に対して０．５〜１０
重量％であり、助剤成分の含有量が、導体成分とムライ
ト粉末と助剤成分の合計量に対して４重量％以下である
ことにある。In order to achieve the above object, the means, the main component
Contains all mullite powder and vitrifying sintering aid
Prepare a green sheet and strike the green sheet
A through hole is provided to remove the conductor component and mud in this through hole.
Contains light powder and vitrified auxiliary components,
With conductive paste prepared in paste form
And then firing
Wherein the content of the mullite powder is
0.5 to 10 with respect to the total amount of the light powder and the conductor component
% By weight, and the content of the auxiliary component is
4% by weight or less based on the total amount of the powder and auxiliary components
It is in.
【００１３】この導体ペーストにおいて望ましいのは、
ムライト粉末として、その平均粒径が３μｍ以下のも
のを用いる場合である。同じく望ましいのは、導体成分
をタングステンＷとするものである。What is desirable in this conductor paste is that
This is the case where mullite powder having an average particle size of 3 μm or less is used. Also desirably, the conductor component is tungsten W.
【００１４】[0014]
【作用】本発明においては、主成分としてのムライト粉
末及びガラス化可能な焼結助剤を含有するグリーンシー
トを準備し、そのグリーンシートを打ち抜いて貫通孔を
設け、この貫通孔の中に上記いずれかの導体ペーストを
充填した後、焼成することによってセラミック配線基板
が製造される。このセラミック配線基板は、単板でも多
層基板でもよい。多層基板の場合は、導体ペーストを充
填した後、複数枚のグリーンシートを積層して焼成す
る。こうして得られるセラミック配線基板は、ムライト
を主成分とし貫通孔を有する絶縁基板と、その貫通孔に
充填された導体柱とを備えた配線基板において、導体柱
が導体成分のほかに少量のムライト及びガラスを含むこ
とを特徴とする。In the present invention, a green sheet containing mullite powder as a main component and a sintering aid which can be vitrified is prepared, and the green sheet is punched to form a through hole. After filling with any of the conductive pastes, firing is performed to manufacture a ceramic wiring board. This ceramic wiring board may be a single board or a multilayer board. In the case of a multi-layer substrate, after filling the conductive paste, a plurality of green sheets are laminated and fired. The ceramic wiring board thus obtained is a wiring board including an insulating substrate having mullite as a main component and having a through hole, and a conductive pillar filled in the through hole, wherein the conductive pillar has a small amount of mullite in addition to the conductive component. It is characterized by containing glass.
【００１５】ここで導体ペーストは、タングステン粉末
やモリブデン粉末のような導体金属の粉末をペースト状
に調製するために溶剤、樹脂等のビヒクルを含んでい
る。従って、導体金属とビヒクルのみからなる導体ペー
ストを貫通孔に充填して焼成すると、ビヒクルが占有し
ていた体積が気孔となるので、得られる導体柱は多孔質
となる。そこで、一般には予め導体ペーストにガラス化
可能な助剤成分を添加しておくと、焼成過程でその助剤
成分がガラス化して液相を構成し、いわゆる液相焼結に
より導体金属の粒子同士を結合し、導体柱の緻密化を達
成する。Here, the conductive paste contains a vehicle such as a solvent or a resin for preparing a conductive metal powder such as a tungsten powder or a molybdenum powder into a paste. Therefore, when the conductor paste consisting of the conductor metal and the vehicle alone is filled into the through-holes and fired, the volume occupied by the vehicle becomes pores, and the resulting conductor pillars are porous. Therefore, generally, when an auxiliary component that can be vitrified is added to the conductor paste in advance, the auxiliary component is vitrified in the firing process to form a liquid phase. And achieve the densification of the conductor pillar.
【００１６】従って、導体ペーストを、導体金属と助剤
との無機混合粉末に溶剤、樹脂等のビヒクルを加え調製
すると、ペースト中の無機成分のみで緻密な導体柱が焼
結できる。この際の、導体ペーストの収縮量は、導体ペ
ースト中の無機粉末が占めていた体積まで収縮すること
になる。Accordingly, when a conductive paste is prepared by adding a vehicle such as a solvent or a resin to an inorganic mixed powder of a conductive metal and an auxiliary agent, a dense conductive column can be sintered only with the inorganic component in the paste. At this time, the amount of contraction of the conductive paste is reduced to the volume occupied by the inorganic powder in the conductive paste.
【００１７】ペースト中のビヒクルが占めている体積
は、溶剤分がシート中に拡散、あるいは揮発し気孔とな
り、また樹脂分が脱脂〜焼成時に分解揮発あるいは酸化
消失したりして気孔となる。そして焼成時導体柱の緻密
化の過程で、気孔の体積分だけ収縮するのである。The volume occupied by the vehicle in the paste is such that the solvent component diffuses or volatilizes into the sheet to form pores, and the resin component decomposes and volatilizes or disappears by oxidation during degreasing to baking to form pores. In the process of densification of the conductor pillars during firing, the conductor pillars contract by the volume of the pores.
【００１８】例えば、導体ペースト中の無機粉末成分
（導体金属と助剤）及びビヒクル分が占める体積率をそ
れぞれ４０％（導体金属＝３０％，助剤＝１０％）及び
６０％とすると、計算上少なくとも４０％の体積にまで
収縮する。これを長さの収縮率に換算すれば（０．４）
1/3＝０．７３７まで長手方向、径方向にそれぞれ短か
くなる。For example, assuming that the volume fractions of the inorganic powder component (conductor metal and auxiliary) and the vehicle in the conductor paste are 40% (conductor metal = 30%, auxiliary = 10%) and 60%, respectively. Shrink to a volume of at least 40% above. If this is converted into the length shrinkage, (0.4)
It becomes shorter in the longitudinal direction and the radial direction until 1/3 = 0.737.
【００１９】グリーンシートの表面に印刷される配線パ
ターンは、その厚さが２０〜３０μｍと薄いのに対し
て、貫通孔はその直径が１００〜３００μｍと大きい。
従って、収縮量の絶対値もかなり大きい。The wiring pattern printed on the surface of the green sheet has a thickness as thin as 20 to 30 μm, whereas the diameter of the through hole is as large as 100 to 300 μm.
Therefore, the absolute value of the contraction amount is also considerably large.
【００２０】一方、絶縁層となるグリーンシートも成形
段階では、導体ペーストと同様に溶剤、樹脂を含んでい
るが、（焼成前の）シート成形時に溶剤分は乾燥により
除去され、その際、体積減少がおきる。従って、グリー
ンシートの収縮量は、シート中の無機成分（ムライト及
び焼結助剤）が占めている体積まで収縮することになる
が、シート成形時に乾燥収縮している分だけ、無機成分
の充填が上がっており、前記のペーストに比べ収縮は小
さい。一般に、シートの長さ方向の収縮率は、シート時
に比べ０．８〜０．８５まで焼成収縮する。On the other hand, the green sheet to be an insulating layer also contains a solvent and a resin at the molding stage, similarly to the conductor paste, but the solvent is removed by drying at the time of molding the sheet (before firing). Decreases. Therefore, the amount of shrinkage of the green sheet shrinks to the volume occupied by the inorganic components (mullite and sintering aid) in the sheet. And shrinkage is smaller than that of the paste. Generally, the shrinkage rate in the length direction of the sheet is shrunk by firing to 0.8 to 0.85 as compared with the sheet.
【００２１】その結果、導体ペーストの収縮量の方がグ
リーンシートの貫通孔の収縮量よりも多くなり、導体柱
と貫通孔との間に間隙が生じる。そこで、本発明では、
予め導体ペーストに少量のムライトを添加しておくこと
によって、絶縁層と導体柱との結合並びに導体柱の緻密
化を達成したのである。As a result, the amount of shrinkage of the conductive paste is larger than the amount of shrinkage of the through hole of the green sheet, and a gap is generated between the conductive pillar and the through hole. Therefore, in the present invention,
By adding a small amount of mullite to the conductor paste in advance, the connection between the insulating layer and the conductor pillar and the densification of the conductor pillar were achieved.
【００２２】すなわち、ガラスの濡れ性は、金属粒子に
対するよりもムライト粉末に対するほうが良い。従っ
て、絶縁層となるグリーンシートに添加されている助剤
成分が、焼成過程でガラス化するとともに、導体柱の中
心まで拡散し、導体金属の焼結を促進する。その結果、
予め導体ペーストに添加される助剤が存在しないか又は
極めて少量であっても導体柱が緻密化する。この為、絶
縁層であるセラミック部より、ガラス化した助剤成分が
導体柱に拡散してきた体積分だけ、導体柱の収縮は減少
する。That is, the wettability of glass is better for mullite powder than for metal particles. Therefore, the auxiliary component added to the green sheet to be an insulating layer is vitrified in the firing process and diffuses to the center of the conductor column, thereby promoting sintering of the conductor metal. as a result,
Even if there is no or very small amount of an auxiliary agent added to the conductor paste in advance, the conductor pillars are densified. For this reason, the shrinkage of the conductor column is reduced by the volume of the vitrified auxiliary component diffused into the conductor column from the ceramic portion as the insulating layer.
【００２３】例えば、導体ペースト中に必要な無機成分
（導体金属、助剤）及びビヒクルの含有量を、前例と同
じく体積率でそれぞれ４０％及び６０％とする。この場
合、実際に用いられる導体ペーストの組成は、体積率
で、導体金属３７％、ムライト３％、及びビヒクル６０
％でよい。導体柱自身の焼結に必要な助剤分１３．３％
は、グリーンシートから供給されるからである。For example, the contents of the necessary inorganic components (conductor metal, auxiliary) and the vehicle in the conductor paste are set to 40% and 60%, respectively, in the same manner as in the previous example. In this case, the composition of the conductor paste actually used is, by volume percentage, conductor metal 37%, mullite 3%, and vehicle 60.
% May be sufficient. 13.3% of auxiliary agent necessary for sintering of conductor pillar itself
Is supplied from the green sheet.
【００２４】そうすると、グリーンシートから供給され
た助剤がビヒクルと置き換えされ、ビヒクルの占める体
積が６０％から４６．７％に低下したこととなる。従っ
て、ビヒクルの占有体積分に起因して導体ペーストが収
縮する量は、計算上５３．３％の体積まで収縮する。こ
れを長さの収縮率に換算すれば（０．５３３）1/3＝８
１．１％となり、グリーンシートの収縮率にマッチす
る。こうして、導体柱の緻密化と同時に導体柱と貫通孔
との間隙が狭まる。Then, the auxiliary supplied from the green sheet is replaced with the vehicle, and the volume occupied by the vehicle is reduced from 60% to 46.7%. Thus, the amount of shrinkage of the conductive paste due to the occupied volume of the vehicle shrinks to a calculated volume of 53.3%. If this is converted into the contraction rate of the length, (0.533) 1/3 = 8
1.1%, which matches the shrinkage ratio of the green sheet. Thus, the gap between the conductor pillar and the through hole is narrowed at the same time as the conductor pillar is densified.
【００２５】但し、導体ペーストに含まれるムライトの
量がムライト粉末と導体成分との合計量に対して０．５
重量％より少ないと、グリーンシートから助剤が浸透す
る作用に乏しい。他方、そのムライトの量が１０重量％
より多くなると、導体柱の電気抵抗が上昇するので好ま
しくない。However, the amount of mullite contained in the conductor paste is 0.5 to the total amount of the mullite powder and the conductor component.
If the amount is less than the weight percentage, the effect of the auxiliary agent penetrating from the green sheet is poor. On the other hand, the amount of mullite is 10% by weight.
If the number is too large, the electric resistance of the conductor columns increases, which is not preferable.
【００２６】また、含有量が同じであるなら、導体ペー
スト中のムライトは、細かいものほど望ましい。その理
由は判然としないが、導体ペースト中のムライト量が同
じならば、細かいものほど導体ペースト中により均一に
分布するので、助剤成分を安定して引き寄せるため、導
体柱の電気抵抗が低くなるものと考えられる。導体成分
としてタングステンＷが望ましい理由は、その熱膨張係
数がムライトセラミックスの熱膨張係数に近いからであ
る。If the content is the same, the finer the mullite in the conductor paste, the better. Although the reason is not clear, if the amount of mullite in the conductive paste is the same, the finer the mullite, the more evenly distributed in the conductive paste, so that the auxiliary component is stably attracted, and the lower the electrical resistance of the conductive column It is considered something. Tungsten W is desirable as a conductor component because its thermal expansion coefficient is close to that of mullite ceramics.
【００２７】尚、本発明導体ペーストは、グリーンシー
トから助剤成分の供給を受けるものであるが、導体成分
と少量のムライト粉末の他に予めガラス化可能な助剤成
分を含んでいる。その助剤成分の含有量を、導体成分と
ムライト粉末と助剤成分の合計量に対して４重量％以下
とする。助剤成分は、ガラス化することによってその体
積の減少を伴うので、４重量％より多いと収縮率が過大
となるからである。望ましい助剤添加量は、２重量％以
下である。The conductor paste of the present invention is supplied with an auxiliary component from the green sheet, and contains an auxiliary component which can be vitrified in advance in addition to the conductor component and a small amount of mullite powder . The content of the auxiliary component is 4% by weight or less based on the total amount of the conductor component, the mullite powder and the auxiliary component. This is because the auxiliary component is accompanied by a decrease in volume due to vitrification, so that if it is more than 4% by weight, the shrinkage becomes excessive. A desirable amount of the additive is 2% by weight or less.
【００２８】[0028]
【実施例】−実施例１− 本発明導体ペーストを用いてセラミック配線基板を製造
した具体例を説明する。セラミック配線基板の製造方法
は、グリーンシートを作製する工程、導体ペーストを調
製する工程及び導体ペーストをグリーンシートに適用し
て加工する工程からなる。そして、製造した後に、種々
の特性が評価された。以下、工程別に説明する。EXAMPLES-Example 1-A specific example of manufacturing a ceramic wiring board using the conductive paste of the present invention will be described. The method for manufacturing a ceramic wiring board includes a step of preparing a green sheet, a step of preparing a conductor paste, and a step of applying and processing the conductor paste to the green sheet. After production, various characteristics were evaluated. Hereinafter, each process will be described.
【００２９】［グリーンシート作製工程］表１に示す種
類の原料粉末を、表１に示す組成で合計重量が１ｋｇに
なるように配合した。原料粉末のうち、シリカ、アルミ
ナ及び塩基性炭酸マグネシウムは、焼結助剤である。[Green Sheet Preparation Step] Raw material powders of the type shown in Table 1 were blended so that the total weight was 1 kg with the composition shown in Table 1. Of the raw material powders, silica, alumina and basic magnesium carbonate are sintering aids.
【００３０】[0030]
【表１】 配合物をアルミナボールミル中で湿式混合し、バインダ
ーとしてブチラール樹脂、可塑剤としてフタル酸ジブチ
ルを加えて更に混合してキャスティング用のスラリーを
得た。このスラリーを真空中で脱泡した後、ドクターブ
レード法によってキャスティングし乾燥した。こうし
て、厚さ０．５ｍｍのグリーンシートを作製した。[Table 1] The mixture was wet-mixed in an alumina ball mill, and butyral resin as a binder and dibutyl phthalate as a plasticizer were added and further mixed to obtain a slurry for casting. The slurry was defoamed in a vacuum, then cast by a doctor blade method and dried. Thus, a green sheet having a thickness of 0.5 mm was produced.
【００３１】［導体ペースト調製工程］平均粒子径２．
０μｍのタングステンＷ粉末、同２．４μｍのムライト
粉末及び焼結助剤を、表２の組成となるように秤量し
た。焼結助剤はグリーンシートを作製した際に用いたも
のと同一である。秤量粉末１００重量部をアセトン２７
重量部とともに樹脂製ボールミルによって湿式混合し
た。更に、エチルセルロース６．１重量部及びブチルカ
ルビトールアセテート７．１重量部を添加して混練し、
アセトンを揮発除去することによって、導体ペーストを
調製した。[Conductor paste preparation step] Average particle size
0 μm of tungsten W powder, 2.4 μm of mullite powder and a sintering aid were weighed to have the composition shown in Table 2. The sintering aid is the same as that used when producing the green sheet. 100 parts by weight of the weighed powder was mixed with acetone 27
The mixture was wet mixed with a weight part by a resin ball mill. Further, 6.1 parts by weight of ethyl cellulose and 7.1 parts by weight of butyl carbitol acetate were added and kneaded,
A conductor paste was prepared by removing acetone by volatilization.
【００３２】［加工工程］前記グリーンシートに直径
０．１２ｍｍ、０．２５ｍｍ又は０．５０ｍｍの貫通孔
をパンチングにより設けた。貫通孔は、直径の３倍のピ
ッチで１０列×１０行の方眼状に合計１００個設けた。
その内訳は、直径０．１２ｍｍの貫通孔が４０個で、直
径０．２５ｍｍの貫通孔及び同０．５０ｍｍの貫通孔が
それぞれ３０個である。[Processing Step] A through hole having a diameter of 0.12 mm, 0.25 mm or 0.50 mm was formed in the green sheet by punching. A total of 100 through holes were provided in a grid of 10 columns × 10 rows at a pitch three times the diameter.
The breakdown is that there are 40 through holes having a diameter of 0.12 mm, and 30 through holes having a diameter of 0.25 mm and 30 through holes having a diameter of 0.50 mm.
【００３３】各々の貫通孔に上記導体ペーストを充填し
た。そして、導体ペーストが充填されたグリーンシート
を４枚積層し、少量の水蒸気を含む水素雰囲気中、温度
１５５０℃で焼成した。導体ペースト及びグリーンシー
トは、それぞれ導体柱及び絶縁層となって、セラミック
基板が得られた。Each of the through holes was filled with the conductive paste. Then, four green sheets filled with the conductive paste were laminated and fired at a temperature of 1550 ° C. in a hydrogen atmosphere containing a small amount of water vapor. The conductor paste and the green sheet became conductor pillars and an insulating layer, respectively, and a ceramic substrate was obtained.
【００３４】［評価］得られたセラミック基板につき、
１００個の導体柱から１０個の導体柱を選別し、それら
導体柱の最上面と最下面との間の抵抗値並びに導体柱の
径及び長さを測定し、比抵抗の値を計算した。また、導
体柱の露出している部分を目視し、セラミック基板表面
に対するその露出面の凹凸の有無を観察した。次にセラ
ミック基板の表面を研磨した後、導体柱の径方向断面の
微細組織を電子顕微鏡で観察した。これら比抵抗値、凹
凸の有無及び微細組織を表２に併記した。比抵抗値は、
１０個のデータの平均値である。[Evaluation] For the obtained ceramic substrate,
Ten conductor pillars were selected from the 100 conductor pillars, the resistance value between the uppermost surface and the lowermost surface of the conductor pillars, the diameter and the length of the conductor pillars were measured, and the specific resistance value was calculated. Further, the exposed portions of the conductor pillars were visually observed, and the presence or absence of irregularities on the exposed surfaces of the ceramic substrate surface was observed. Next, after polishing the surface of the ceramic substrate, the fine structure of the cross section in the radial direction of the conductor column was observed with an electron microscope. Table 2 also shows these specific resistance values, the presence or absence of irregularities, and the fine structure. The specific resistance value is
This is the average value of 10 data.
【００３５】[0035]
【表２】 表２にみられるように、本発明範囲に属するセラミック
基板は、導体柱の露出面の高さがセラミック基板の表面
の高さとほぼ同じであった。そして、ガラス化した助剤
が導体柱の中心まで浸透しており、導体柱が均一な組織
になっていた。参考のためにＮｏ．３の導体柱の金属組
織状態を図１に示す。図において円形の内側が導体柱で
あり、外側がセラミック基板である。また、ムライトの
含有量が１０重量％以下であれば、抵抗値も５０μΩと
低かった。[Table 2] As seen from Table 2, in the ceramic substrate belonging to the scope of the present invention, the height of the exposed surface of the conductor pillar was almost the same as the height of the surface of the ceramic substrate. Then, the vitrified auxiliary penetrated to the center of the conductor pillar, and the conductor pillar had a uniform structure. No. for reference. FIG. 1 shows the metallographic structure of the third conductor column. In the figure, the inside of the circle is the conductor column, and the outside is the ceramic substrate. When the mullite content was 10% by weight or less, the resistance value was as low as 50 μΩ.
【００３６】これに対してタングステンのみからなる導
体柱（Ｎｏ．１）及びムライトが添加されず且つ助剤量
の少ない導体柱（Ｎｏ．７）は、セラミック基板の表面
よりも突出していた。そして、これらの導体柱の微細組
織は不均一であった。参考のためにＮｏ．１の導体柱の
金属組織状態を図２に示す。図において円形の内側が導
体柱であり、外側がセラミック基板である点では、図１
と同様であるが、導体中が緻密な外周部と緻密でない中
心部とに分相している。従って、導体柱が突出したの
は、グリーンシートの中の助剤が中心部まで浸透してお
らず、焼結不十分であったためであると考察される。ま
た、同じくムライトが添加されず且つ助剤量の少ない導
体柱（Ｎｏ．４）は、セラミック基板の表面より突出し
てはいなかったものの、その組織が不均一であった。On the other hand, the conductor pillar (No. 1) consisting only of tungsten and the conductor pillar (No. 7) to which mullite was not added and the amount of the auxiliary agent was small protruded from the surface of the ceramic substrate. And the microstructure of these conductor columns was non-uniform. No. for reference. FIG. 2 shows the state of the metal structure of the first conductor column. 1 in that the inside of the circle is a conductor column and the outside is a ceramic substrate.
However, the inside of the conductor is divided into a dense outer peripheral portion and a less dense central portion. Therefore, it is considered that the reason why the conductor pillars protruded was that the auxiliary in the green sheet did not penetrate to the central portion and was insufficiently sintered. Similarly, the conductor column (No. 4) to which mullite was not added and the amount of the auxiliary agent was small did not protrude from the surface of the ceramic substrate, but had a non-uniform structure.
【００３７】他方、ムライトが添加されず且つ助剤量が
過剰である導体柱（Ｎｏ．１１，１５，１６，２０〜２
２）は、セラミック基板の表面よりも窪んでいた。これ
らの導体柱の微細組織は、均一であった。就中、Ｎｏ．
１５，１６，２０〜２２の導体柱は、亀裂を生じてい
た。従って、導体ペーストに含まれていた助剤がガラス
化して焼結を過度に促進したものと考察される。On the other hand, conductor columns (Nos. 11, 15, 16, 20 to 2) in which mullite was not added and the amount of the auxiliary was excessive.
2) was recessed from the surface of the ceramic substrate. The microstructure of these conductor columns was uniform. Especially, No.
15, 16, 20 to 22 conductor pillars had cracks. Therefore, it is considered that the auxiliary contained in the conductive paste was vitrified and excessively promoted sintering.
【００３８】−実施例２− 導体ペーストに添加されるムライト粉末として平均粒子
径１．７μｍのものを用いた以外は実施例１と同一条件
でセラミック配線基板を製造した。実施例１と同様に評
価した結果を表３に示す。Example 2 A ceramic wiring board was manufactured under the same conditions as in Example 1 except that mullite powder having an average particle diameter of 1.7 μm was added to the conductive paste. Table 3 shows the results of the evaluation performed in the same manner as in Example 1.
【００３９】[0039]
【表３】 表３にみられるように、本例のセラミック基板も、導体
柱の露出面の高さがセラミック基板の表面の高さとほぼ
同じであった。そして、ガラス化した助剤が導体柱の中
心まで浸透しており、導体柱が均一な組織になってい
た。また、実施例１と本例とで、タングステン及びムラ
イトの含有量が同じもの同志で比較すれば、全般的に本
例の導体柱のほうが低抵抗であった。[Table 3] As can be seen from Table 3, in the ceramic substrate of this example, the height of the exposed surface of the conductor pillar was almost the same as the height of the surface of the ceramic substrate. Then, the vitrified auxiliary penetrated to the center of the conductor pillar, and the conductor pillar had a uniform structure. In addition, when the same content of tungsten and mullite was compared between Example 1 and the present example, the conductor pillar of the present example generally had lower resistance.
【００４０】[0040]
【発明の効果】以上のように本発明の導体ペーストによ
れば、ムライトセラミック基板の表面から突出すること
も窪むこともない適性な導体柱が得られる。従って、断
線及び気密不良が生じにくく、しかも高精度に表面配線
を形成したセラミック配線基板を提供することができ
る。As described above, according to the conductor paste of the present invention, a suitable conductor pillar which does not protrude or dent from the surface of the mullite ceramic substrate can be obtained. Therefore, it is possible to provide a ceramic wiring board in which disconnection and poor airtightness hardly occur and surface wiring is formed with high precision.
【図１】実施例１のＮｏ．３の導体柱の金属組織を示す
概念図である。FIG. It is a conceptual diagram which shows the metal structure of the 3rd conductor pillar.
【図２】実施例１のＮｏ．１の導体柱の金属組織を示す
概念図である。FIG. It is a conceptual diagram which shows the metallographic structure of one conductor pillar.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｈ０５Ｋ 3/46 Ｈ０５Ｋ 3/46 Ｎ Ｓ (56)参考文献 特開 昭63−122195（ＪＰ，Ａ) 特開 平４−155994（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H05K 1/09 H01B 1/16 H05K 1/11 H05K 3/40 H05K 3/46 Continuation of the front page (51) Int.Cl. 7 Identification symbol FI H05K 3/46 H05K 3/46 NS (56) References JP-A-63-122195 (JP, A) JP-A-4-155994 (JP, A) (58) Field surveyed (Int.Cl. 7 , DB name) H05K 1/09 H01B 1/16 H05K 1/11 H05K 3/40 H05K 3/46
Claims (3)
可能な焼結助剤を含有するグリーンシートを準備し、そ
のグリーンシートを打ち抜いて貫通孔を設け、この貫通
孔の中に、導体成分とムライト粉末とガラス化可能な助
剤成分とを含み、ビヒクルによってペースト状に調製さ
れた導体ペーストを充填した後、焼成することを特徴と
するセラミック配線基板の製造方法であって、ムライト
粉末の含有量が、そのムライト粉末と導体成分との合計
量に対して０．５〜１０重量％であり、助剤成分の含有
量が、導体成分とムライト粉末と助剤成分の合計量に対
して４重量％以下であることを特徴とする製造方法。 [Claim 1] preparing a green sheet containing the mullite powder and vitrifiable sintering aid as a main component, a through hole is formed by punching out the green sheet, in the through hole, and the conductor components Mullite powder and vitrification aid
A method for producing a ceramic wiring board, comprising: filling a conductive paste prepared in a paste form with a vehicle , comprising the steps of:
The powder content is the sum of the mullite powder and the conductor component
0.5 to 10% by weight based on the amount, and contains auxiliary components
The amount is based on the total amount of the conductor component, mullite powder and auxiliary component.
The production method is not more than 4% by weight.
粒径３μｍ以下のものである請求項１に記載の製造方
法。 Mullite powder wherein the conductive paste, prepared side of claim 1 is the following average particle diameter of 3μm
Law.
である請求項１又は２に記載の製造方法。 3. The conductor component of the conductor paste is tungsten W.
The method according to claim 1, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10510593A JP3162539B2 (en) | 1993-04-05 | 1993-04-05 | Method of manufacturing ceramic wiring board having conductor formed by conductor paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10510593A JP3162539B2 (en) | 1993-04-05 | 1993-04-05 | Method of manufacturing ceramic wiring board having conductor formed by conductor paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06291435A JPH06291435A (en) | 1994-10-18 |
| JP3162539B2 true JP3162539B2 (en) | 2001-05-08 |
Family
ID=14398588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10510593A Expired - Fee Related JP3162539B2 (en) | 1993-04-05 | 1993-04-05 | Method of manufacturing ceramic wiring board having conductor formed by conductor paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3162539B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4699225B2 (en) | 2006-01-31 | 2011-06-08 | 株式会社トクヤマ | Metallized ceramic substrate manufacturing method, metallized ceramic substrate manufactured by the method, and package |
| WO2014181697A1 (en) * | 2013-05-08 | 2014-11-13 | 株式会社村田製作所 | Multi-layer wiring board |
| KR20180121509A (en) | 2016-03-11 | 2018-11-07 | 엔지케이 인슐레이터 엘티디 | Connecting board |
| KR20180121508A (en) | 2016-03-11 | 2018-11-07 | 엔지케이 인슐레이터 엘티디 | Method for manufacturing connection board |
| KR20180121507A (en) | 2016-03-11 | 2018-11-07 | 엔지케이 인슐레이터 엘티디 | Connecting board |
-
1993
- 1993-04-05 JP JP10510593A patent/JP3162539B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06291435A (en) | 1994-10-18 |
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